supporting information for alkene-assisted cis-to-trans ...similar to cis-to-trans isomerization of...

S1

Supporting Information for

Alkene-assisted cis-to-trans isomerization of polyunsaturated alkenes

Alexey V. Smarun,a Fedor Duzhin,b Milena Petkovićc and Dragoslav Vidović*a,d

a School of Physical and Mathematical Sciences, Division of Chemistry and Biological Chemistry, Nanyang Technological University, 21 Nanyang Link, Singapore, 637371

b School of Physical and Mathematical Sciences, Division of Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, Singapore, 637371

c Faculty of Physical Chemistry, University of Belgrade, Studentski Trg 12-16, 11000 Belgrade, Republic of Serbia d Current Address: School of Chemistry, Monash University, Melbourne, Australia

Table of contents

I. Derivation of the formula for the extent of trans isomerization in skipped poly-alkenes. ............................................ S2

II. Expanded Table 1 from the manuscript. .................................................................................................................... S3

III. Isomerization of E-Lin with complex 1 in DCM-d2 at r.t. ........................................................................................... S4

IV. Isomerization of E-Lnn with complex 1 in DCM-d2 at r.t. ........................................................................................ S6

V. Isomerization of O-Lnn with complex 1 in DCM-d2 at r.t. ......................................................................................... S8

VI. Isomerization of H-Lnn with complex 1 in DCM-d2 at r.t. ...................................................................................... S10

VII. Isomerization of E-Ara with complex 1 in DCM-d2 at r.t. ...................................................................................... S12

VIII. Isomerization of E-DHA with complex 1 in DCM-d2 at r.t. ................................................................................... S14

IX. Isomerization of O-DHA with complex 1 in DCM-d2 at r.t. ..................................................................................... S16

X. Isomerization of H-DHA with complex 1 in DCM-d2 at r.t. ...................................................................................... S18

XI. Isomerization of T-Lnn with complex 1 in DCM-d2 at r.t. ....................................................................................... S20

XII. Isomerization of POLY with complex 1 in DCM-d2 at r.t. ...................................................................................... S22

XIII. Isomerization of M-Ole with complex 1 in acetone-d6 at 60 ˚C ........................................................................... S24

XIV. Computational details. .......................................................................................................................................... S26

XV. References. ........................................................................................................................................................... S34

Electronic Supplementary Material (ESI) for Dalton Transactions.This journal is © The Royal Society of Chemistry 2017

S2

I. Derivation of the formula for the extent of trans isomerization in skipped poly-alkenes.

Let's say that we have 𝑛 molecules in our mixture and 𝑚 double bonds in each molecule. Combined 1H and 13C NMR spectroscopic data allows us to determine following parameters:

• 𝑎, the fraction of bis-allylic positions in our mixture that are surrounded by two trans bonds.

• 𝑏, the fraction of bis-allylic positions in our mixture that are surrounded by one trans and one cis double bonds.

• 𝑐, the fraction of mono-allylic positions in our mixture that are next to trans bonds.

Besides, 𝑚 is known but 𝑛 is not known and may be very large. We need to find the fraction of trans-bonds 𝑡 given 𝑎,

𝑏, 𝑐, and 𝑚.

We will represent the sample as a 𝑛 × 𝑚 matrix 𝑀 where each entry corresponds to a bond and each row to a molecule.

Let also 0 represent a cis-bond and 1 - a trans-bond. We will use dot products of columns of the matrix 𝑀 to find 𝑡.

Let 𝑥𝑖 be the 𝑖-th column of 𝑀 for each 𝑖 = 1,… ,𝑚 and let 𝑒 be the vector of dimension 𝑛 all of whose entries are 1. Further, let 𝐴 be the total number of bis-allylic positions with trans-trans bonds, let 𝐵 be the total number of bis-allylic

positions with cis-trans bonds, let 𝐶 be the total number of mono-allylic positions by trans-bonds, and let 𝑇 be the total number of trans-bonds, i.e.,

𝑎 =𝐴

𝑛(𝑚 − 1), 𝑏 =

𝐵

𝑛(𝑚 − 1), 𝑐 =

𝐶

2𝑛, 𝑡 =

𝑇

𝑚𝑛

Then, since we only have ones and zeroes in 𝑀, the dot product 𝑒 ⋅ 𝑥𝑖 is exactly the number of ones in 𝑥𝑖 and total number of trans-bonds in our mixture is

𝑇 = 𝑒 ⋅∑𝑥𝑖

𝑚

𝑖=1

In a similar manner, we have

𝐶 = 𝑒 ⋅ (𝑥1 + 𝑥𝑚),

𝐴 = ∑ 𝑥𝑖

𝑚−1

𝑖=1

⋅ 𝑥𝑖+1,

𝐵 = ∑(𝑒 − 𝑥𝑖)

𝑚−1

𝑖=1

⋅ 𝑥𝑖+1 + ∑ 𝑥𝑖

𝑚−1

𝑖=1

⋅ (𝑒 − 𝑥𝑖+1) = 𝑒 ⋅ (𝑥1 + 2∑ 𝑥𝑖

𝑚−1

𝑖=2

+ 𝑥𝑚) − 2 ∑ 𝑥𝑖

𝑚−1

𝑖=1

⋅ 𝑥𝑖+1

= 2𝑒 ⋅∑𝑥𝑖

𝑚

𝑖=1

− 𝑒 ⋅ (𝑥1 + 𝑥𝑚) − 2 ∑ 𝑥𝑖

𝑚−1

𝑖=1

⋅ 𝑥𝑖+1

Therefore, we get 𝐵 = 2𝑇 − 𝐶 − 2𝐴, or, equivalently, 𝑇 = 𝐴 +𝐵

2+

𝐶

2. Finally,

𝑡 =𝑇

𝑚𝑛=

𝐴

𝑚𝑛+

𝐵

2𝑚𝑛+

𝐶

2𝑚𝑛=2(𝑚 − 1)𝑎 + (𝑚 − 1)𝑏 + 2𝑐

2𝑚

S3

II. Expanded Table 1 from the manuscript.

Parameters presented in the table:

• 𝑎, the fraction of bis-allylic positions in the mixture that are surrounded by two trans bonds.

• 𝑏, the fraction of bis-allylic positions in the mixture that are surrounded by one trans and one cis double bonds.

• 𝑐, the fraction of mono-allylic positions in the mixture that are next to trans bonds.

• 𝑡, the extent of trans isomerization (% of trans bonds in the mixture).

Substrate Cat. %

Time, h

1H NMR data 13C NMR data mean parameters

t a b c a b c a b c

1 E-Lin 1 72 5 76 43 5 76 43 43

2 E-Lnn 1 4 0 80 78 0 78 75 0 79 77 52

3 A-Lnn 1 24 1 49 48 1 49 48 32

4 O-Lnn 1 24 4 80 81 3 82 84 4 81 83 57

5 H-Lnn 1 24 0 78 77 0 78 78 0 78 78 52

6 E-Ara 2 18 24 n.d. n.d. 25 67 75 25 67 75 63

7 E-DHA 3 18 33 n.d. n.d. 34 58 73 34 58 73 65

8 A-DHA 3 24 31 n.d. n.d. 31 47 58 31 47 58 55

9 O-DHA 3 24 29 n.d. n.d. 31 65 78 30 65 78 65

10 H-DHA 3 8 34 n.d. n.d. 36 59 79 35 59 79 67

11 E-Lin 1 24 1 54 28 1 54 28 28

12 E-Lin-d4 1 24 2 28 16 2 28 16 16

13 T-Lnn 3 18 0 73 72 0 73 74 0 73 73 49

14 POLY 1a 24 n.a. n.a. n.d. n.a. n.a. 80 n.a. n.a. 80 80

15 M-Ole 5b 48 n.a. n.a. 38 n.a. n.a. 37c n.a. n.a. 37 37

n.d. = not determined due to peak overlap; n.a. = not available due to absence of such position in the substrate; aWith

respect to the repeating unit. bReaction was carried in acetone-d6 and was heated to 60 ˚C. cFormation of positional

isomers.

S4

III. Isomerization of E-Lin with complex 1 in DCM-d2 at r.t. (entry 1, Table 1)

Figure S1: 1H NMR spectra (500 MHz, DCM-d2) of reaction mixture: a) full spectra; b) sections of 1H-NMR spectra (expanded between 6.0–0.5 ppm) for greater clarity.*

*From this point on, all 1H NMR spectra will be presented in a similar fashion due to the appearance of all significant spectral information within the specified range.

a)

b)

S5

1H NMR spectrum of E-Lin consists of three key elements: vinylic protons that resonate as a multiplet at 5.32-5.45 ppm, bis-allylic protons that occur as a triplet at 2.82 ppm and mono-allylic protons – as a quartet at 2.07-2.12 ppm (Figure S1). Addition of complex 1 to the solution of E-Lin in DCM-d2 initiates cis-to-trans isomerization of substrate’s double bonds that, in turn, results in several changes of 1H NMR spectra that follow the characteristic trend of such process. First of all, while the vinylic multiplet at 5.32-5.45 ppm partially decreases in size another multiplet appears on its low-frequency side at 5.39-5.50 ppm indicating partial isomerization of cis-double bonds to trans.

Protons of allylic positions that are surrounded by newly formed trans-double bonds should resonate upfield to original peaks on proton spectra. Indeed, a new multiplet appears at 1.98-2.04 ppm indicating mono-allylic protons by newly formed trans-double bonds. Integration shows that after 24 hours of reaction time just about 1 mono-allylic proton out of 4 (about 28%) has a trans-double bond next to it (labelled as “E-mono-allylic” for subsequent discussion). After 72 hours the fraction of E-mono-allylic protons reaches 43%.

Likewise, two new triplets are formed for bis-allylic protons at 2.76 and 2.70 ppm. However, when reaction reaches equilibrium after 72 hours the peak at 2.70 ppm represents not more than 5% of all bis-allylic protons. The fact that this peak occurs exactly where bis-allylic protons of ethyl linolelaidate (trans,trans-9,12-octadecadienoate) resonate suggests that in general only one of two double bonds in E-Lin is isomerized. Cis-to-trans isomerization of either double bond in E-Lin forms a bis-allylic position surrounded by one cis-double bond and one trans-double bond. Such position resonates at 2.76 ppm: exactly between the original bis-allylic position surrounded by two cis-double bonds (labelled as “(Z,Z)-bis-allylic” for subsequent discussion) and the bis-allylic position surrounded by two trans-double bonds (labelled as “(E,E)-bis-allylic” for subsequent discussion). Such bis-allylic position represents either cis,trans- or trans,cis-system (labelled as “(E,Z)/(Z,E)-bis-allylic” for subsequent discussion) and reaction mixture most probably consists of both isomers. Integration of this newly formed peak at 2.76 ppm after 24 hours of reaction time indicates that the fraction of (E,Z)/(Z,E)-bis-allylic positions in the reaction mixture reaches 54%, and after 72 hours the percentage of such positions in the equilibrium mixture equals 76%. Combined evidence suggest that the resulting equilibrium mixture is mostly composed of (E,Z)- and (Z,E)-E-Lin isomers with traces of (E,E)-E-Lin isomer. Such mixture composition contains 43% of trans-double bonds.

S6

IV. Isomerization of E-Lnn with complex 1 in DCM-d2 at r.t. (entry 2, Table 1)

Figure S2: 1H NMR spectra (500 MHz, DCM-d2) of reaction mixture.

Key elements of 1H NMR spectrum of E-Lnn are as follows: vinylic protons resonate as a multiplet at 5.33-5.46 ppm, bis-allylic protons occur as a triplet at 2.85 ppm and mono-allylic protons – as a multiplet at 2.08-2.15 ppm (Figure S2). Similar to cis-to-trans isomerization of E-Lin, addition of complex 1 to the solution of E-Lnn results in partial reduction of original vinylic and allylic peaks followed by appearing of a new multiplet at 5.48-5.56 ppm, a triplet at 2.77 ppm and a multiplet at 1.99-2.07 ppm. Based on peak integration around 80% of bis-allylic positions and around 78% of mono-allylic positions are converted into new configurations by the time the equilibrium is established. The fact that only one new triplet at 2.77 ppm could be observed for bis-allylic protons suggests that no (E,E)-bis-allylic positions were formed. Further evidence for this theory could be obtained from the analysis of 13C NMR spectra.

Figure S3b illustrates selected sections of 13C NMR spectra of pure E-Lnn and equilibrium mixture after 4 hours of reaction time. Mono-allylic carbon atoms of E-Lnn occur as two singlets at 27.16 and 20.50 ppm and its bis-allylic carbon atoms - as two singlets at 25.55 and 25.46 ppm. In a course of cis-to-trans isomerization of E-Lnn all four original peaks for allylic carbons diminish in size while several new peaks appear at 32.48, 30.38-30.26 and 25.52 ppm.

Examination of 13C NMR data for all 8 possible geometric isomers of E-Lnn from the literature1 indicates that as one double bond next to allylic carbon atom changes its configuration from cis to trans its carbon resonance is shifted downfield by approximately 5 ppm. These are the cases of E-mono-allylic and (E,Z)/(Z,E)-bis-allylic carbon atoms. When both double bonds around bis-allylic carbon atom obtain trans-configuration its chemical shift appears downfield by about 10 ppm as in the case of (E,E)-bis-allylic carbon atoms.

Following this logic, it can be clearly seen that by the time the equilibrium is established two singlets for original Z-mono-allylic carbon atoms at 27.16 and 20.50 ppm are diminished in size while two new singlets have appeared for E-mono-allylic carbon atoms at 32.48 and 25.52 ppm, respectively. Integration of these peaks indicates that by the time the equilibrium is established around 75% of all mono-allylic positions have trans-double bonds beside them.

Meanwhile, while two singlets for original (Z,Z)-bis-allylic carbon atoms at 25.55 and 25.46 ppm are diminished in size, only one set of new peaks about 5 ppm downfield from them could be observed: 30.38, 30.35, 30.31 and 30.26 ppm. These peaks indicate newly formed (E,Z)/(Z,E)-bis-allylic carbon atoms. The fact that no new peaks were found in the 35-36 ppm range strongly suggests an absence of (E,E)-bis-allylic carbon atoms in the equilibrium mixture supporting our previous examination of 1H NMR spectra. Integration of bis-allylic carbon atom peaks indicates that around 78% of

S7

all (Z,Z)-bis-allylic positions were transformed into (E,Z)/(Z,E)-bis-allylic positions only. Averaging the parameters obtained from the examination of both 1H and 13C NMR spectra results is 77% E-mono-allylic and 79% (E,Z)/(Z,E)-bis-allylic positions. Such mixture composition contains 52% of trans-double bonds.

It is strongly strongly believed that obtained equilibrium mixture is mainly composed of (t,c,t) (i.e. trans,cis,trans or 9E,12Z,15E) isomer of E-Lnn and virtually has no (t,t,t), (t,t,c) or (c,t,t) isomers in it.

Figure S3: 13C{1H} NMR spectra (125.7 MHz, DCM-d2) of substrate and reaction mixture. a) full spectra; b) sections of 13C{1H} NMR spectra (expanded between 40.0–20.0 ppm) for greater clarity.*

*From this point on, all 13C{1H} NMR spectra will be presented in a similar fashion because crucial spectral information discussed in text appears within the specified range.

a)

b)

S8

V. Isomerization of O-Lnn with complex 1 in DCM-d2 at r.t. (entry 4, Table 1)


Isomerization of alcohol O-Lnn with complex 1 resulted in the similar outcome as did its ester analogue E-Lnn. By the

time the equilibrium was established about 80% of bis-allylic and 81% of mono-allylic positions were converted into new

configurations. Also, due to the presence of a minor peak at 2.72 ppm there seems to be just a small amount of (E,E)-

bis-allylic positions presented in the equilibrium mixture – about 4% (Figure S4). Further evidence for this theory could

be obtained from the analysis of 13C NMR spectra.

S9

Figure S5: Sections of 13C{1H} NMR spectra (125.7 MHz, DCM-d2) of substrate and reaction mixture.

Figure S5 illustrates selected sections of 13C NMR spectra of pure O-Lnn and equilibrium mixture after 24 hours of reaction time. Similar to the reaction of E-Lnn, in a course of cis-to-trans isomerization of O-Lnn two singlets for original Z-mono-allylic carbon atoms at 27.20 and 20.50 ppm are diminished in size while two new singlets have appeared for E-mono-allylic carbon atoms at 32.51 and 25.53 ppm. Integration of these peaks indicates that around 84% of all mono-allylic positions have trans-double bonds beside them. Meanwhile, two singlets for original (Z,Z)-bis-allylic carbon atoms at 25.56 and 25.46 ppm are diminished in size producing one major set of new peaks about 5 ppm downfield from them: 30.36, 30.31 and 30.27 ppm. These peaks indicate formation of (E,Z)/(Z,E)-bis-allylic positions. A very small peak is observed at 35.53 ppm pointing at the minor presence of (E,E)-bis-allylic carbon atoms in the equilibrium mixture supporting our previous examination of 1H NMR spectra. Integration of bis-allylic carbon atom peaks indicates that by the time the equilibrium is established around 82% of all (Z,Z)-bis-allylic positions were transformed into (E,Z)/(Z,E)-bis-allylic positions, while about 3% - into (E,E)-bis-allylic positions. Averaging the parameters obtained from the examination of both 1H and 13C NMR spectra results is 83% E-mono-allylic, 81% (E,Z)/(Z,E)-bis-allylic and 4% (E,E)-bis-allylic positions. Such mixture composition contains 57% of trans-double bonds.

Same as for E-Lnn, it is strongly believed that obtained equilibrium mixture is mainly composed of (t,c,t) isomer of O-Lnn and has just a minor amount of (t,t,t), (t,t,c) or (c,t,t) isomers in it.

S10

VI. Isomerization of H-Lnn with complex 1 in DCM-d2 at r.t. (entry 5, Table 1)


Isomerization of hydrocarbon H-Lnn with complex 1 resulted in the similar outcome as for both E-Lnn and O-Lnn. By the time the equilibrium was established about 77% of bis-allylic and 78% of mono-allylic positions were converted into new configurations. Similar to reaction of E-Lnn, only one new triplet at 2.77 ppm could be observed for bis-allylic protons indicating that virtually no (E,E)-bis-allylic positions were formed in a course of cis-to-trans isomerization of H-Lnn (Figure S6). Further evidence for this theory could be obtained from the analysis of 13C NMR spectra.

S11


Figure S7 illustrates selected sections of 13C NMR spectra of pure H-Lnn and equilibrium mixture after 24 hours of reaction time. Similar to reaction of E-Lnn, in a course of cis-to-trans isomerization of H-Lnn two singlets for original Z-mono-allylic carbon atoms at 27.21 and 20.50 ppm are diminished in size while two new singlets have appeared for E-mono-allylic carbon atoms at 32.52 and 25.52 ppm. Integration of these peaks indicates that around 78% of all mono-allylic positions have trans-double bonds beside them. Meanwhile, two singlets for original (Z,Z)-bis-allylic carbon atoms at 25.55 and 25.46 ppm are diminished in size producing only one set of new peaks about 5 ppm downfield from them: 30.38, 30.36, 30.31 and 30.26 ppm. No new peaks were found in the 35-36 ppm range which strongly suggests absence of (E,E)-bis-allylic carbon atoms in the equilibrium mixture supporting our previous examination of 1H NMR spectra. Integration of bis-allylic carbon atom peaks indicates that by the time the equilibrium is established around 78% of all (Z,Z)-bis-allylic positions were transformed only into (E,Z)/(Z,E)-bis-allylic positions. Averaging the parameters obtained from the examination of both 1H and 13C NMR spectra results is 78% E-mono-allylic and 78% (E,Z)/(Z,E)-bis-allylic positions. Such mixture composition contains 52% of trans-double bonds.

Same as for E-Lnn, it is strongly believed that obtained equilibrium mixture is mainly composed of (t,c,t) isomer of H-Lnn and virtually has no (t,t,t), (t,t,c) or (c,t,t) isomers in it.

S12

VII. Isomerization of E-Ara with complex 1 in DCM-d2 at r.t. (entry 6, Table 1)


Key elements of 1H NMR spectrum of E-Ara are as follows: bis-allylic protons occur as several peaks at 2.80-2.89 ppm and mono-allylic protons – as a two quartets at 2.08 and 2.12 ppm (Figure S8). Addition of complex 1 to the solution of E-Ara results in diminishing of areas of original allylic peaks followed by appearing of a multiplet at 2.78 for (E,Z)/(Z,E)-bis-allylic protons, a multiplet at 2.71 ppm for (E,E)-bis-allylic protons as well as two multiplets at 2.06 and 2.01 ppm for E-mono-allylic protons. It is impossible to estimate the extent of cis-to-trans isomerization of mono-allylic positions using 1H NMR data due to severe peak overlapping. However, the fraction of (E,E)-bis-allylic positions in the equilibrium mixture can be estimated as about 24% of overall number of bis-allylic positions by integrating a multiplet at 2.71 ppm.

S13


Figure S9 illustrates selected sections of 13C NMR spectra of pure E-Ara and equilibrium mixture after 18 hours of

reaction time. Similar to the reactions of cis-to-trans isomerization of E-Lnn, O-Lnn and H-Lnn described above,

reaction between E-Ara and complex 1 results in diminished size of original Z-mono-allylic carbon atom peaks at 27.17

and 26.53 ppm followed by appearance of new sets of peaks at 32.49-32.50 and 31.83-31.84 ppm corresponding to E-

mono-allylic carbon atoms. Integration of these peaks indicates that around 75% of all mono-allylic positions have trans-

double bonds beside them in the equilibrium mixture. At the same time a set of peaks for original (Z,Z)-bis-allylic carbon

atoms at 25.57-25.58 ppm is also diminished in size. However, unlike the cases of E-Lnn, O-Lnn and H-Lnn described

above, instead of mainly producing only a single set of peaks at 30.26-30.34 ppm corresponding to (E,Z)/(Z,E)-bis-allylic

carbon atoms, the formation of an intensive set of peaks is observed about 10 ppm downfield from original peaks. These

new peaks at 35.48 and 35.52 ppm indicate the considerable presence of (E,E)-bis-allylic carbon atoms in the

equilibrium mixture. Integration of bis-allylic carbon atom peaks indicates that by the time the equilibrium is established

around 67% of all (Z,Z)-bis-allylic positions were transformed into (E,Z)/(Z,E)-bis-allylic positions and 25% - into (E,E)-

bis-allylic positions supporting our previous examination of 1H NMR spectra. Averaging the parameters obtained from

the examination of both 1H and 13C NMR spectra results is 75% E-mono-allylic, 67% (E,Z)/(Z,E)- and 25% (E,E)-bis-

allylic positions. Such mixture composition contains 63% of trans-double bonds.

Following the logic as for the cases of E-Lnn, O-Lnn and H-Lnn, it is believed that obtained equilibrium mixture is mainly composed of (t,t,c,t) and (t,c,t,t) isomers of E-Ara, i.e. one internal cis-double bond must remain intact.

S14

VIII. Isomerization of E-DHA with complex 1 in DCM-d2 at r.t. (entry 7, Table 1)


Key elements of 1H NMR spectrum of E-DHA are as follows: bis-allylic protons occur as several peaks at 2.81-2.88 ppm and mono-allylic protons – as a two multiplets at 2.09 and 2.37 ppm (Figure S10). Similar to the case of E-Ara, cis-to-trans isomerization of E-DHA results in diminishing of areas of original allylic peaks followed by appearing of a multiplet at 2.78 for (E,Z)/(Z,E)-bis-allylic protons, a multiplet at 2.73 ppm for (E,E)-bis-allylic protons as well as two multiplets at 2.34 and 2.05 ppm for E-mono-allylic protons. It is impossible to estimate the extent of cis-to-trans isomerization of mono-allylic positions using 1H NMR data due to severe peak overlapping. However, the amount (E,E)-bis-allylic positions in the equilibrium mixture can be estimated as about 33% of overall number of bis-allylic positions by integrating a multiplet at 2.73 ppm.

S15


Figure S11 illustrates selected sections of 13C NMR spectra of pure E-DHA and equilibrium mixture after 18 hours of

reaction time. Reaction of cis-to-trans isomerization of E-DHA follows the same trend as E-Ara. Original Z-mono-allylic

carbon atom peaks at 22.77 and 20.50 ppm are diminished in size and new peaks appear at 27.84 and 25.52 ppm

corresponding to E-mono-allylic carbon atoms. Integration of these peaks indicates that around 73% of all mono-allylic

positions have trans-double bonds beside them in the equilibrium mixture. At the same time a set of peaks for original

(Z,Z)-bis-allylic carbon atoms at 25.47- 25.59 ppm is also diminished in size while we observe one set of peaks at 30.21-

30.33 ppm corresponding to (E,Z)/(Z,E)-bis-allylic carbon atoms and another at 35.40-35.51 ppm indicating the

presence of (E,E)-bis-allylic carbon atoms. Integration of all bis-allylic carbon atom peaks indicates that by the time the

equilibrium is established around 58% of all (Z,Z)-bis-allylic positions were transformed into (E,Z)/(Z,E)-bis-allylic

positions and 34% - into (E,E)-bis-allylic positions supporting our previous examination of 1H NMR spectra. Averaging

the parameters obtained from the examination of both 1H and 13C NMR spectra results is 73% E-mono-allylic, 58%

(E,Z)/(Z,E)- and 34% (E,E)-bis-allylic positions. Such mixture composition contains 65% of trans-double bonds.

It is believed that obtained equilibrium mixture is mainly composed of isomers of E-DHA that have all their double bonds in the trans-configuration except of one of its inner ones: (t,t,t,t,c,t), (t,t,t,c,t,t), (t,t,c,t,t,t), and (t,c,t,t,t,t).

S16

IX. Isomerization of O-DHA with complex 1 in DCM-d2 at r.t. (entry 9, Table 1)


Key elements of 1H NMR spectrum of O-DHA are as follows: bis-allylic protons occur as several peaks at 2.82-2.96 ppm and mono-allylic protons – as a group of multiplets at 2.08-2.20 ppm (Figure S12). Similar to the cases of E-Ara and E-DHA, cis-to-trans isomerization of O-DHA results in diminishing of areas of original allylic peaks followed by appearing of a multiplet at 2.80 for (E,Z)/(Z,E)-bis-allylic protons, a multiplet at 2.74 ppm for (E,E)-bis-allylic protons as well as a new set of multiplets at 2.02- 2.14 ppm for E-mono-allylic protons. It is impossible to estimate the extent of cis-to-trans isomerization of mono-allylic positions using 1H NMR data due to severe peak overlapping. However, the amount (E,E)-bis-allylic positions in the equilibrium mixture can be estimated as about 29% of overall number of bis-allylic positions by integrating a multiplet at 2.74 ppm.

S17


Figure S13 illustrates selected sections of 13C NMR spectra of pure O-DHA and equilibrium mixture after 24 hours of

reaction time. Reaction of cis-to-trans isomerization of O-DHA follows the same trend as E-DHA. Original Z-mono-allylic

carbon atom peaks at 23.54 and 20.52 ppm are diminished in size and new peaks appear at 28.82 and 25.53 ppm

corresponding to E-mono-allylic carbon atoms. Integration of these peaks indicates that around 78% of all mono-allylic

positions have trans-double bonds beside them in the equilibrium mixture. At the same time a set of peaks for original

(Z,Z)-bis-allylic carbon atoms at 25.48- 25.60 ppm is also diminished in size while we observe one set of peaks at 30.27-

30.34 ppm corresponding to (E,Z)/(Z,E)-bis-allylic carbon atoms and another at 35.47-35.50 ppm indicating the

presence of (E,E)-bis-allylic carbon atoms. Integration of all bis-allylic carbon atom peaks indicates that by the time the

equilibrium is established around 65% of all (Z,Z)-bis-allylic positions were transformed into (E,Z)/(Z,E)-bis-allylic

positions and 31% - into (E,E)-bis-allylic positions supporting our previous examination of 1H NMR spectra. Averaging

the parameters obtained from the examination of both 1H and 13C NMR spectra results is 78% E-mono-allylic, 65%

(E,Z)/(Z,E)- and 31% (E,E)-bis-allylic positions. Such mixture composition contains 65% of trans-double bonds.

It is strongly believed that reaction of cis-to-trans isomerization of O-DHA produces similar equilibrium mixture as E-DHA.

S18

X. Isomerization of H-DHA with complex 1 in DCM-d2 at r.t. (entry 10, Table 1)


Key elements of 1H NMR spectrum of H-DHA are as follows: bis-allylic protons occur as several peaks at 2.86-2.90 ppm and mono-allylic protons – as a group of multiplets at 2.07-2.15 ppm (Figure S14). Similar to the cases of E-DHA and O-DHA, cis-to-trans isomerization of H-DHA results in diminishing of areas of original allylic peaks followed by appearing of a multiplet at 2.79 for (E,Z)/(Z,E)-bis-allylic protons, a multiplet at 2.73 ppm for (E,E)-bis-allylic protons as well as a new set of multiplets at 1.98- 2.08 ppm for E-mono-allylic protons. It is impossible to estimate the extent of cis-to-trans isomerization of mono-allylic positions using 1H NMR data due to severe peak overlapping. However, the amount (E,E)-bis-allylic positions in the equilibrium mixture can be estimated as about 34% of overall number of bis-allylic positions by integrating a multiplet at 2.73 ppm.

S19


Figure S15 illustrates selected sections of 13C NMR spectra of pure H-DHA and equilibrium mixture after 8 hours of

reaction time. Reaction of cis-to-trans isomerization of H-DHA follows the same trend as E-DHA and O-DHA. Original

Z-mono-allylic carbon atom peaks at 29.25 and 20.51 ppm are diminished in size and new peaks appear at 34.62-34.64

and 25.53 ppm corresponding to E-mono-allylic carbon atoms. Integration of these peaks indicates that around 79% of

all mono-allylic positions have trans-double bonds beside them in the equilibrium mixture. At the same time a set of

peaks for original (Z,Z)-bis-allylic carbon atoms at 25.47- 25.59 ppm is also diminished in size while we observe one set

of peaks at 30.21-30.35 ppm corresponding to (E,Z)/(Z,E)-bis-allylic carbon atoms and another at 35.46-35.53 ppm

indicating the presence of (E,E)-bis-allylic carbon atoms. Integration of all bis-allylic carbon atom peaks indicates that

by the time the equilibrium is established around 59% of all (Z,Z)-bis-allylic positions were transformed into (E,Z)/(Z,E)-

bis-allylic positions and 36% - into (E,E)-bis-allylic positions supporting our previous examination of 1H NMR spectra.

Averaging the parameters obtained from the examination of both 1H and 13C NMR spectra results is 79% E-mono-allylic,

59% (E,Z)/(Z,E)- and 35% (E,E)-bis-allylic positions. Such mixture composition contains 67% of trans-double bonds.

It is strongly believed that reaction of cis-to-trans isomerization of H-DHA produces similar equilibrium mixture as E-DHA and O-DHA.

S20

XI. Isomerization of T-Lnn with complex 1 in DCM-d2 at r.t. (entry 13, Table 1)


Isomerization of triglyceride T-Lnn with complex 1 resulted in the similar outcome as for its ester analogue E-Lnn. By

the time the equilibrium was established about 73% of bis-allylic and 72% of mono-allylic positions were converted into

new configurations (Figure S16).

S21

Figure S17: Sections of 13C{1H} NMR spectra (125.7 MHz, DCM-d2) of reaction mixture.

Figure S17 illustrates selected sections of 13C NMR spectra of pure T-Lnn and equilibrium mixture after 18 hours of reaction time. Similar to the reaction of E-Lnn, in a course of cis-to-trans isomerization of T-Lnn two singlets for original Z-mono-allylic carbon atoms at 27.22 and 20.55 ppm are diminished in size while two new singlets have appeared for E-mono-allylic carbon atoms at 32.54 and 25.58 ppm. Integration of these peaks indicates that around 74% of all mono-allylic positions have trans-double bonds beside them. Meanwhile, two singlets for original (Z,Z)-bis-allylic carbon atoms at 25.60 and 25.51 ppm are diminished in size producing one major set of new peaks about 5 ppm downfield from them: 30.43, 30.40, 30.36 and 30.32 ppm. These peaks indicate formation of (E,Z)/(Z,E)-bis-allylic positions. Integration of bis-allylic carbon atom peaks indicates that by the time the equilibrium was established around 73% of all (Z,Z)-bis-allylic positions were transformed into (E,Z)/(Z,E)-bis-allylic positions. No peaks are observed about 10 ppm downfield to singlets for original (Z,Z)-bis-allylic carbon atoms indicating that no (E,E)-bis-allylic carbon atoms are presented in the equilibrium mixture. Averaging the parameters obtained from the examination of both 1H and 13C NMR spectra results is 73% E-mono-allylic and 73% (E,Z)/(Z,E)-bis-allylic positions. Such mixture composition contains 49% of trans-double bonds.

Similar to E-Lnn, it is strongly believed that obtained equilibrium mixture is mainly composed of (t,c,t) isomer of T-Lnn.

S22

XII. Isomerization of POLY with complex 1 in DCM-d2 at r.t. (entry 14, Table 1)


Key elements of 1H NMR spectrum of POLY are as follows: vinylic protons appear as a group of multiplets at 5.39-5.62

ppm and mono-allylic protons – as a group of multiplets at 1.91-2.05 ppm (Figure S18). Cis-to-trans isomerization of

POLY results in diminishing of areas of original allylic and vinylic peaks followed by appearance of multiplets at lower

and higher frequencies to the original resonances, respectively. It is impossible to estimate the extent of cis-to-trans

isomerization of POLY positions using 1H NMR data due to severe peak overlapping. More data could be obtained from

the analysis of 13C NMR spectra.

S23


Figure S19 illustrates selected sections of 13C NMR spectra of pure POLY and equilibrium mixture after 24 hours of reaction time. Reaction of cis-to-trans isomerization of POLY follows the same trend as was described before. Original Z-mono-allylic carbon atom peak at 27.40 ppm is diminished in size and new peak appears at 32.72 ppm corresponding to E-mono-allylic carbon atoms. Integration of these peaks indicates that around 80% of all mono-allylic positions have trans-double bonds beside them in the equilibrium mixture which means that about 80% of all double bonds in the substrate have been isomerized to trans.

S24

XIII. Isomerization of M-Ole with complex 1 in acetone-d6 at 60 ˚C (entry 15, Table 1)

Figure S20: 1H NMR spectra (500 MHz, acetone-d6) of reaction mixture.

Key elements of 1H NMR spectrum of M-Ole are as follows: vinylic protons appear as a broadened peak at 5.30-5.42

ppm and mono-allylic protons – as a multiplet at 2.00-2.10 ppm (overlapping with acetone-d6 residual peak; Figure S20).

Cis-to-trans isomerization of M-Ole results in diminishing of areas of original allylic and vinylic peaks followed by

appearance of multiplets at lower and higher frequencies to the original resonances, respectively. Integration of these

new peaks allowed us to estimate that around 38% of all mono-allylic positions in M-Ole have trans-double bonds beside

them in the equilibrium mixture.

S25

Figure S21: Sections of 13C{1H} NMR spectra (125.7 MHz, DCM-d2) of substrate and isolated product mixture.

Figure S21 illustrates selected sections of 13C NMR spectra of pure M-Ole and equilibrium mixture after 48 hours of reaction time. Reaction of cis-to-trans isomerization of M-Ole follows the similar trend as was described before. Original Z-mono-allylic carbon atom peaks at 27.15 and 27.11 ppm are diminished in size and new peaks corresponding to E-mono-allylic carbon atoms appear about 5 ppm downfield to them. However, here the similarity between cis-to-trans isomerization of M-Ole and other examples involving poly-alkenes discussed above ends. Instead of producing only a single pair of singlets for two E-mono-allylic carbon atoms about 5 ppm downfield to original peaks, a large group of peaks appears at 31.74-32.57 ppm. Meanwhile, instead of simply diminishing in size, two original singlets at 27.15 and 27.11 ppm completely transform into a large set of peaks at 26.28-26.95 ppm. Similar pattern could be observed for vinilyc peaks as well. In contrast to cis-to-trans isomerization of poly-alkenes, this unusual behaviour suggests that isomerization of M-Ole led to migration of its double bond along a carbon chain and formation of a complicated mixture of positional isomers.

S26

XIV. Computational details.

Quantum chemical calculations were performed on the model substrate (x=n=1, R=R'=Me, Table 1) with the

Gaussian092 program package by employing the B3LYP3,4 functional. In all calculations, LANL2DZ basis set modified

by Couty and Hall5 was used for the ruthenium atom. Optimization of all stationary points was performed in the gas

phase with the 6-31G** basis set employed for the alkene's carbon and hydrogen atoms, and 3-21G basis set for Cp

and Cp* atoms.

Species int1 and ts12 (see below) were also optimized in the presence of the solvent, DCM, which was incorporated

through the polarizable continuum method (PCM) as implemented in the Gaussian suite of programs6-8. Due to the small

differences between bond lengths of the structures optimized in the gas phase and in DCM, Table S1, all geometry

optimizations were performed in the gas phase.

In order to obtain more reliable values for activation energies, single point energy calculations were performed on all

optimized structures at the B2GP-PLYP9,10/6-311G**(C,H)-LANL2DZ(Ru) level in the presence of DCM, (see Figure

S22).

Table S1. Selected bond lengths (in Å) of species int1 and ts12 formed in a reaction with Cp*. DCM was used as a

solvent.

gas/PCM

int1 ts12

C29-Ru 2.312/2.304 2.348/2.336

C30-Ru 2.312/2.310 2.313/2.311

C32-Ru 2.363/2.361 2.320/2.321

C33-Ru 2.187/2.187 2.193/2.192

C34-Ru 2.481/2.480 2.308/2.306

Table S2. Energies of partially optimized structures (with respect to int1) for fixed C-H bond lengths obtained when one

of the bis-allylic H atoms of int1 was moved towards the lace at the Ru centre as observed in int2.

r(C-H) / Å E / kcal/mol

1.092 (int1)

0.0

1.200 4.5

1.300 13.0

1.400 23.6

1.500 34.9

1.600 46.3

1.700 57.3

S27

Figure S22: Optimized geometries of the key intermediates and transition states for cis-trans isomerization of a bis-

olefin.

S28

Figure S23: Electronic energy in kcal/mol (with respect to int2) computed at B3LYP/3-21G(Cp*)-6-31G**(alkene)-

LANL2DZ(Ru) level along the reaction path from ts12 to int2 (reaction with Cp*). Partial optimization was performed for

fixed C-H bond lengths. Blue stars represent stationary points.

Selected Cp*/Cp WBIs computed with the B3LYP functional and 3-21G(Cp*/Cp), 6-31G*(alkene) and LANL2DZ(Ru)

basis sets.

int1 ts12 int2 ts23 int3 ts34 int4

C29-Ru 0.383/0.401 0.369/0.384 0.348/0.365 0.345/0.357 0.370/0.385 0.433/0.445 0.397/0.414

C30-Ru 0.332/0.349 0.341/0.358 0.336/0.356 0.351/0.374 0.361/0.375 0.396/0.406 0.366/0.383

C32-Ru 0.338/0.363 0.423/0.438 0.435/0.448 0.646/0.648 0.522/0.525 0.483/0.499 0.325/0.349

C33-Ru 0.396/0.418 0.329/0.342 0.284/0.301 0.230/0.245 0.309/0.315 0.372/0.380 0.356/0.391

C34-Ru 0.180/0.213 0.407/0.420 0.472/0.476 0.052/0.047 0.464/0.468 0.320/0.326 0.011/0.011

C29-C30 1.473/1.452 1.462/1.445 1.468/1.448 1.451/1.431 1.438/1.424 1.425/1.417 1.454/1.428

C32-C33 1.460/1.430 1.357/1.343 1.335/1.326 1.098/1.108 1.257/1.256 1.339/1.331 1.506/1.469

C33-C34 1.041/1.049 1.223/1.224 1.296/1.287 1.850/1.856 1.339/1.331 1.183/1.178 1.022/1.020

NOTE: Labelling of atoms in the xyz files are not the same, but C29 is always refereed to the static carbon atom at the

end of the alkene fragment.

Selected Cp*/Cp bond lengths in Å computed with the B3LYP functional and 3-21G(Cp*/Cp), 6-31G*(alkene) and

LANL2DZ(Ru) basis sets.

int1 ts12 int2 ts23 int3 ts34 int4

C29-Ru 2.312/2.313 2.348/2.347 2.373/2.368 2.374/2.376 2.368/2.364 2.324/2.326 2.183/2.175

C30-Ru 2.312/2.308 2.313/2.309 2.326/2.319 2.302/2.297 2.314/2.316 2.248/2.252 2.330/2.327

C32-Ru 2.363/2.353 2.320/2.317 2.320/2.317 2.168/2.175 2.228/2.236 2.217/2.218 2.335/2.316

C33-Ru 2.187/2.176 2.193/2.191 2.218/2.214 2.322/2.314 2.206/2.207 2.203/2/202 2.377/2.337

C34-Ru 2.481/2.443 2.308/2.309 2.296/2.299 3.597/3.587 2.306/2.312 2.318/2.323 3.383/3.316

C29-C30 1.392/1.393 1.391/1.392 1.389/1.391 1.392/1.394 1.396/1.397 1.405/1.405 1.393/1.395

C32-C33 1.392/1.395 1.407/1.408 1.410/1.411 1.450/1.444 1.421/1.421 1.410/1.410 1.383/1.388

C33-C34 1.495/1.491 1.433/1.432 1.416/1.416 1.339/1.338 1.407/1.407 1.446/1.447 1.509/1.512

S29

Reaction with Cp*: optimized structures

int1:

44 0.039583 0.554855 0.418501 6 2.602439 3.942013 -1.548873

6 0.479381 0.018111 2.621428 6 1.530151 3.272386 -0.667818

6 1.675854 -0.144544 1.837447 6 1.563175 1.766349 -0.829132

6 1.403887 -1.155783 0.823560 6 0.807800 1.003866 -1.715563

6 0.038630 -1.609024 0.999780 6 -0.520034 1.384653 -2.334486

6 -0.539578 -0.867857 2.104701 6 -1.435055 0.584094 -1.427948

6 -1.887676 -1.120505 2.723402 6 -1.994254 1.028107 -0.233157

6 -0.623176 -2.732170 0.252745 6 -1.671454 2.351278 0.383865

6 2.418666 -1.756012 -0.108396 6 -2.590307 2.775745 1.530425

6 3.013921 0.471654 2.140693 1 -2.668927 1.989972 2.286250

6 0.332680 0.924312 3.810693 1 -2.223609 3.683390 2.015696

1 0.973700 1.805599 3.721411 1 -3.594323 2.980081 1.147338

1 -0.701279 1.256294 3.937493 1 -0.590561 2.327738 0.828297

1 0.625473 0.386085 4.722348 1 -1.574098 3.142706 -0.364960

1 -2.288344 -0.219426 3.196524 1 -2.757320 0.420047 0.244708

1 -1.805163 -1.895190 3.497037 1 -1.729209 -0.402173 -1.777140

1 -2.611111 -1.469287 1.980513 1 -0.720138 2.457768 -2.289793

1 -1.704484 -2.583731 0.180848 1 -0.600888 1.069623 -3.377382

1 -0.449502 -3.679947 0.779971 1 1.206062 0.047813 -2.043355

1 -0.219885 -2.831959 -0.758479 1 2.522035 1.330794 -0.556708

1 1.940295 -2.227912 -0.970951 1 1.716578 3.531105 0.381082

1 2.993335 -2.528368 0.419870 1 0.549717 3.682927 -0.925593

1 3.128139 -1.006794 -0.472823 1 3.604671 3.579115 -1.299507

1 3.529836 -0.118368 2.909727 1 2.425697 3.739979 -2.609641

1 2.909816 1.494652 2.513972 1 2.593308 5.025930 -1.402599

1 3.655879 0.493549 1.255947

ts12:

44 -0.071470 0.063937 0.029642 6 -2.966395 1.818227 0.226686

6 -0.108921 -0.066594 2.317121 6 -1.901318 1.268168 -0.695860

6 1.263045 -0.001904 1.857137 6 -1.948594 -0.108718 -1.090527

6 1.525284 -1.205766 1.082143 6 -1.002167 -0.680173 -1.960758

6 0.319372 -1.986329 1.047530 6 -0.080321 0.086884 -2.889988

6 -0.700667 -1.274671 1.796936 6 1.101132 0.237637 -1.955961

6 -0.758569 0.893829 3.274757 6 1.427953 1.370536 -1.218497

6 2.292416 1.000540 2.303199 6 1.085510 2.804213 -1.567090

6 2.866331 -1.615197 0.538686 6 2.212281 3.439494 -2.403856

6 0.160291 -3.352216 0.437913 1 -2.639637 2.734391 0.724012

6 -2.068759 -1.803134 2.132479 1 -3.859904 2.062652 -0.359853

1 -2.781143 -0.991269 2.304105 1 -3.254770 1.092757 0.991166

1 -2.459175 -2.444569 1.336728 1 -1.551002 1.976761 -1.440251

1 -2.020943 -2.404315 3.050048 1 -2.659204 -0.766635 -0.596583

1 -0.860520 -3.516517 0.080567 1 -1.035724 -1.759661 -2.080162

1 0.847329 -3.500728 -0.399473 1 0.164983 -0.486089 -3.787127

1 0.377033 -4.121944 1.190596 1 -0.504816 1.042354 -3.205859

1 2.767003 -2.355222 -0.260141 1 1.759057 -0.625210 -1.905394

1 3.467876 -2.066414 1.338654 1 2.338273 1.285219 -0.628146

1 3.425125 -0.757814 0.150491 1 0.949289 3.384482 -0.648050

1 3.101740 1.096582 1.574078 1 0.149263 2.872581 -2.128445

1 2.738004 0.678532 3.253683 1 2.349115 2.911260 -3.352427

1 1.848867 1.988557 2.453753 1 1.976911 4.483864 -2.627670

1 -0.337671 1.897973 3.178267 1 3.166072 3.419861 -1.866823

1 -1.837853 0.954435 3.113057 1 -0.501762 1.596211 0.260230

1 -0.591746 0.553731 4.305414

S30

int2:

44 0.113600 -0.036756 -0.075292 6 2.618135 1.327955 -1.826087

6 -0.035655 0.018428 2.262211 6 1.120725 1.291350 -1.653645

6 1.360547 0.097717 1.862990 6 0.480240 2.070767 -0.660528

6 1.693863 -1.113092 1.160161 6 -0.909937 2.014599 -0.431761

6 0.490249 -1.931572 1.088186 6 -1.954517 1.539175 -1.423190

6 -0.564641 -1.231648 1.797127 6 -2.018748 0.089545 -0.995591

6 -0.752479 1.021124 3.124486 6 -1.403752 -0.977339 -1.638129

6 2.330686 1.167447 2.283799 6 -1.048840 -1.055882 -3.108490

6 3.070025 -1.529964 0.720469 6 -2.219690 -1.658391 -3.908408

6 0.423817 -3.351309 0.595063 1 -1.951146 -1.745720 -4.964954

6 -1.935737 -1.779965 2.080969 1 -2.477026 -2.658761 -3.545694

1 1.836343 2.135206 2.409685 1 -3.115000 -1.033248 -3.836213

1 2.782636 0.898287 3.247730 1 -0.808060 -0.072090 -3.520420

1 3.140024 1.282252 1.557610 1 -0.160737 -1.682005 -3.242181

1 3.665295 -0.670854 0.400833 1 -1.585328 -1.952454 -1.189280

1 3.593622 -2.012011 1.556684 1 -2.640158 -0.110592 -0.127492

1 3.024196 -2.242293 -0.107066 1 -2.907234 2.057640 -1.292886

1 1.120480 -3.519621 -0.230241 1 -1.636837 1.668860 -2.459651

1 0.686141 -4.039000 1.409819 1 -1.278520 2.497182 0.469525

1 -0.581801 -3.610733 0.252276 1 1.093722 2.586377 0.074329

1 -0.390213 2.037852 2.946065 1 0.567857 1.075038 -2.560926

1 -0.579538 0.789017 4.183879 1 0.857185 -0.828499 -1.225611

1 -1.831781 1.002664 2.950620 1 2.891380 2.140482 -2.511087

1 -1.897877 -2.435454 2.960984 1 3.135327 1.503673 -0.879269

1 -2.313956 -2.374978 1.243873 1 2.995482 0.398469 -2.258919

1 -2.652405 -0.981626 2.292654

ts23:

44 0.049423 0.084160 0.146247 6 -3.577769 -0.630626 -2.820988

6 -0.033280 0.289662 2.437882 6 -2.437582 -0.985878 -1.848107

6 1.340244 0.031331 2.076035 6 -1.922674 0.262758 -1.163069

6 1.808207 1.124744 1.252053 6 -0.940295 1.116306 -1.657758

6 0.717928 2.050879 1.075138 6 0.106940 0.730523 -2.690308

6 -0.439655 1.521806 1.790313 6 1.103348 0.068223 -1.748013

6 0.809311 3.408317 0.434419 6 0.956714 -1.342151 -1.445834

6 -1.746751 2.235529 1.996538 6 1.130894 -2.473521 -2.140391

6 -0.847648 -0.505517 3.421817 6 0.866258 -3.863553 -1.652435

6 2.180482 -1.111621 2.573655 1 -4.402980 -0.130070 -2.304343

6 3.221488 1.310188 0.775473 1 -3.976422 -1.537623 -3.284276

1 3.834384 1.730518 1.583657 1 -3.230169 0.032778 -3.619337

1 3.672612 0.359087 0.475716 1 -2.809815 -1.686819 -1.094132

1 3.270651 2.000411 -0.071077 1 -1.635242 -1.498394 -2.382874

1 1.481033 3.405996 -0.428673 1 -2.636449 0.720698 -0.480553

1 1.200507 4.129964 1.164076 1 -0.956644 2.157363 -1.352669

1 -0.170968 3.768793 0.111281 1 0.526065 1.616087 -3.171875

1 -2.021702 2.832072 1.121577 1 -0.263546 0.059104 -3.470275

1 -1.669291 2.916642 2.854351 1 2.090380 0.517026 -1.656282

1 -2.556109 1.528837 2.198691 1 0.633197 -1.594842 -0.342952

1 -1.918060 -0.400820 3.230591 1 1.529598 -2.377142 -3.150595

1 -0.645103 -0.142940 4.438177 1 0.156630 -4.373448 -2.314465

1 -0.594664 -1.567891 3.383711 1 1.785376 -4.460706 -1.663316

1 1.571087 -1.998076 2.768412 1 0.458344 -3.874833 -0.637329

1 2.673084 -0.827600 3.513124 1 -1.157744 -0.881317 0.540162

1 2.959246 -1.377082 1.853506

S31

int3:

44 -0.038728 -0.107950 0.085177 6 -4.311383 -1.008658 -1.839575

6 0.057790 0.112133 2.380963 6 -2.867630 -1.309968 -1.393785

6 1.410708 -0.010819 1.888535 6 -2.264783 -0.092255 -0.723237

6 1.693544 1.139479 1.046009 6 -1.535177 0.919384 -1.349231

6 0.521036 1.962487 1.012732 6 -0.747911 0.767577 -2.643841

6 -0.501436 1.316441 1.824519 6 0.518356 0.177444 -2.052579

6 -0.591506 -0.778602 3.406297 6 0.530415 -1.208806 -1.739517

6 2.420813 -1.012688 2.369939 6 1.394730 -1.710258 -0.749434

6 3.033412 1.478984 0.453608 6 1.375454 -3.155043 -0.335109

6 0.422267 3.334805 0.403636 1 -4.342100 -0.196306 -2.572466

6 -1.840814 1.904615 2.171986 1 -4.938620 -0.719779 -0.990111

1 -1.677740 -0.795682 3.288687 1 -4.758640 -1.895164 -2.297964

1 -0.226229 -1.805420 3.328308 1 -2.285421 -1.622808 -2.264136

1 -0.363051 -0.409169 4.414507 1 -2.872529 -2.152351 -0.695255

1 1.951325 -1.967823 2.619049 1 -2.813027 0.217924 0.164252

1 2.902807 -0.629948 3.279769 1 -1.584083 1.922040 -0.939315

1 3.205967 -1.191067 1.630493 1 -0.577217 1.734946 -3.118317

1 3.569763 0.584918 0.119838 1 -1.225892 0.110274 -3.376234

1 3.660093 1.975125 1.206586 1 1.440001 0.751877 -2.059366

1 2.934709 2.159381 -0.397010 1 -0.250292 -1.858197 -2.121691

1 1.022015 3.417906 -0.507194 1 2.333434 -1.184747 -0.591140

1 0.793127 4.081159 1.118866 1 1.619370 -3.275566 0.722696

1 -0.611289 3.599963 0.163860 1 2.133846 -3.709091 -0.903263

1 -1.724704 2.623447 2.993963 1 0.402241 -3.616091 -0.520167

1 -2.284532 2.440640 1.327085 1 -0.836715 -1.424707 0.465303

1 -2.541575 1.132890 2.501221

ts34:

44 -0.043784 0.032895 0.090659 6 1.548604 -3.511692 -2.627081

6 0.019382 -0.086887 2.380749 6 0.743317 -2.231136 -2.337573

6 1.388326 -0.019930 1.876292 6 0.692932 -1.963704 -0.842570

6 1.552012 1.232751 1.209944 6 -0.385792 -2.188027 0.029561

6 0.285157 1.966982 1.324847 6 -1.884981 -2.152095 -0.308267

6 -0.632684 1.166665 2.072283 6 -2.101016 -0.639372 -0.390797

6 -0.520377 -1.139141 3.310590 6 -1.520477 -0.066561 -1.541560

6 2.458313 -1.046395 2.120137 6 -0.906066 1.233487 -1.695305

6 2.834975 1.782189 0.645311 6 -0.480382 1.672941 -3.092096

6 0.070393 3.389460 0.888564 1 1.095735 -4.382516 -2.143037

6 -2.006621 1.577717 2.524501 1 2.578338 -3.422704 -2.266063

1 -0.370783 -0.818593 4.350437 1 1.587199 -3.704429 -3.703088

1 -1.591893 -1.302169 3.161912 1 1.213927 -1.391047 -2.861494

1 -0.002814 -2.094260 3.187269 1 -0.258359 -2.354688 -2.760400

1 2.063577 -2.066269 2.070469 1 1.670363 -2.086090 -0.378321

1 2.885036 -0.904665 3.121880 1 -0.159887 -2.512150 1.039068

1 3.269664 -0.954302 1.393549 1 -2.145343 -2.670484 -1.237824

1 3.465492 0.985446 0.242248 1 -2.464458 -2.607448 0.496475

1 3.398007 2.296031 1.435663 1 -2.781861 -0.116118 0.271691

1 2.644547 2.501846 -0.154965 1 -1.247680 -0.758207 -2.331278

1 0.430014 4.072147 1.669808 1 -1.299724 2.049558 -1.093051

1 0.620527 3.618320 -0.028996 1 -1.366693 2.013678 -3.637892

1 -0.989552 3.607341 0.725532 1 -0.022852 0.855963 -3.655717

1 -2.483408 2.252104 1.806677 1 0.225849 2.505295 -3.049918

1 -1.940194 2.107505 3.484035 1 0.462459 0.918221 -1.256781

1 -2.656328 0.710082 2.670692

int4:

S32

44 0.134988 -0.444206 0.129465 6 2.448612 -2.606005 -1.685074

6 0.201392 -0.240906 2.361967 6 1.022605 -2.091600 -1.475769

6 1.561896 -0.414432 1.893393 6 0.345075 -2.585086 -0.239811

6 1.889850 0.728030 1.067657 6 -1.020900 -2.462958 0.002723

6 0.747598 1.598058 1.005189 6 -2.056086 -1.995890 -0.999697

6 -0.314105 0.987440 1.793103 6 -1.985811 -0.489491 -0.846097

6 -0.504838 -1.114676 3.359582 6 -1.224727 0.330027 -1.660127

6 2.525765 -1.474861 2.352236 6 -1.459923 1.811327 -1.823474

6 3.226919 0.998647 0.438232 6 -2.386581 2.089385 -3.022781

6 0.752605 2.991239 0.441010 1 2.430740 -3.680858 -1.886911

6 -1.629056 1.625361 2.142848 1 3.063218 -2.437200 -0.796689

1 -0.280158 -0.767192 4.377069 1 2.927529 -2.110409 -2.532787

1 -1.589222 -1.079342 3.225133 1 1.122739 -0.921363 -1.434971

1 -0.179684 -2.156417 3.284790 1 0.406578 -2.224433 -2.371167

1 2.007092 -2.398025 2.626935 1 0.960865 -3.097801 0.494015

1 3.071579 -1.124543 3.238132 1 -1.385745 -2.832882 0.956967

1 3.263211 -1.710948 1.579479 1 -1.819093 -2.311607 -2.020734

1 3.755425 0.070832 0.203015 1 -3.047940 -2.384358 -0.756957

1 3.852985 1.572366 1.135119 1 -2.667665 -0.037722 -0.129465

1 3.123532 1.583806 -0.479586 1 -0.740119 -0.137109 -2.518359

1 1.228257 3.672021 1.159835 1 -1.907970 2.224922 -0.914513

1 1.314728 3.047589 -0.495895 1 -3.367874 1.626183 -2.881788

1 -0.259092 3.356519 0.257793 1 -1.960820 1.700680 -3.953620

1 -2.008124 2.239562 1.322094 1 -2.533583 3.165970 -3.148556

1 -1.502164 2.276992 3.017801 1 -0.508542 2.328513 -1.980826

1 -2.385181 0.875174 2.390859

Reaction with Cp: optimized structures

int1:

44 -0.066835 -0.037262 -0.013469 6 -2.044111 1.169890 -0.788580

6 -0.011892 0.027064 2.304795 6 -3.250151 1.553825 0.069586

6 1.325406 0.014217 1.799022 1 -3.321566 0.919832 0.957298

6 1.500295 -1.216052 1.053987 1 -3.189146 2.594893 0.394447

6 0.267221 -1.955360 1.122502 1 -4.168772 1.434654 -0.512134

6 -0.677337 -1.174893 1.881487 1 -1.095495 1.524008 -0.175972

1 -1.678891 -1.472666 2.148715 1 -1.949308 1.807077 -1.672395

1 0.092818 -2.933101 0.700284 1 -2.630914 -0.963724 -0.644416

1 2.415955 -1.556052 0.595102 1 -0.993396 -1.868064 -2.166016

1 2.081105 0.760293 1.985506 1 -0.545951 0.989986 -3.209990

1 -0.450934 0.814423 2.899491 1 0.133251 -0.508165 -3.860116

6 2.110287 3.422810 -2.292263 1 1.743205 -0.710021 -2.004135

6 1.019989 2.695909 -1.480513 1 2.348352 1.155810 -0.681023

6 1.414378 1.255054 -1.231653 1 0.885289 3.209155 -0.521689

6 1.077649 0.148836 -2.009169 1 0.068857 2.766474 -2.015908

6 -0.110160 0.025740 -2.939169 1 3.073166 3.401733 -1.772449

6 -1.011683 -0.789570 -2.033383 1 2.246764 2.962032 -3.275169

6 -1.928413 -0.280466 -1.113712 1 1.834092 4.470167 -2.442530

ts12:

44 0.015061 -0.036106 -0.033863 6 1.205680 2.595100 -1.773754

6 -0.005455 -0.016599 2.263287 6 2.341711 3.164934 -2.645390

6 1.357181 -0.015418 1.800324 1 -2.522943 2.675117 0.526217

6 1.586408 -1.266710 1.113800 1 -3.762547 1.940808 -0.492570

6 0.373131 -2.019915 1.144602 1 -3.127549 1.049893 0.901178

6 -0.620516 -1.240507 1.839707 1 -1.460921 1.800299 -1.604033

1 -0.474629 0.761524 2.845377 1 -2.573590 -0.892675 -0.613044

S33

1 2.095491 0.743528 2.004283 1 -0.953049 -1.967468 -2.037892

1 2.524506 -1.592568 0.690841 1 0.249642 -0.798223 -3.813414

1 0.229944 -3.008330 0.735443 1 -0.404282 0.767174 -3.314353

1 -1.627657 -1.554873 2.065356 1 1.841196 -0.855524 -1.927509

6 -2.857952 1.731256 0.090646 1 2.441802 1.113248 -0.751653

6 -1.813253 1.132455 -0.823501 1 1.080347 3.226881 -0.888142

6 -1.861689 -0.262902 -1.140940 1 0.269324 2.644196 -2.337008

6 -0.915777 -0.883205 -1.979347 1 2.469836 2.583041 -3.563138

6 0.010067 -0.174843 -2.949393 1 2.119148 4.197989 -2.926430

6 1.190599 0.009672 -2.020778 1 3.295099 3.162817 -2.107840

6 1.532910 1.179304 -1.347837 1 -0.387510 1.509592 0.089626

int2:

44 -0.048335 0.025783 0.020506 6 -1.428884 -0.857529 -2.957533

6 -0.013154 -0.028369 2.375308 6 -2.677296 -1.378340 -3.696191

6 1.340137 0.010786 1.874930 1 -2.476879 -1.449128 -4.768760

6 1.563421 -1.174743 1.104580 1 -2.962495 -2.374333 -3.343222

6 0.332683 -1.933936 1.093486 1 -3.532831 -0.711192 -3.553704

6 -0.629095 -1.223020 1.898834 1 -1.162066 0.124339 -3.358089

1 -0.469288 0.706191 3.021372 1 -0.585407 -1.525041 -3.160510

1 2.075882 0.766930 2.101271 1 -1.894033 -1.782543 -1.031585

1 2.491861 -1.469004 0.640938 1 -2.803686 0.074759 0.133664

1 0.192289 -2.903966 0.643542 1 -3.034252 2.283213 -0.961124

1 -1.632610 -1.552441 2.121743 1 -1.848508 1.869248 -2.207773

6 2.424671 1.330562 -1.799645 1 -1.296656 2.590791 0.721249

6 0.936157 1.366797 -1.566529 1 1.050880 2.596322 0.206758

6 0.380220 2.131658 -0.512274 1 0.330746 1.212162 -2.453165

6 -0.998545 2.125660 -0.214476 1 0.574597 -0.698814 -1.235656

6 -2.115424 1.727081 -1.158957 1 2.711157 2.168944 -2.447034

6 -2.218322 0.271592 -0.760264 1 2.988071 1.417509 -0.867136

6 -1.693283 -0.804890 -1.467386 1 2.729640 0.411871 -2.305602

ts23:

44 0.001839 0.003606 -0.018023 6 -0.011364 -0.580043 -3.556816

6 -0.018274 -0.039038 2.226586 6 -1.160698 -1.429669 -3.999179

6 1.368866 -0.012312 1.808793 1 -1.444302 4.322799 -2.043630

6 1.641068 -1.231058 1.106715 1 -2.805782 4.145606 -0.926371

6 0.436503 -2.012763 1.084387 1 -3.026511 3.804710 -2.646244

6 -0.580840 -1.293405 1.795208 1 -2.861873 1.658796 -1.405701

1 -0.514320 0.702933 2.832607 1 -1.492991 1.827395 -2.491049

1 2.082602 0.763111 2.039786 1 -1.493462 2.347252 0.556030

1 2.590419 -1.527024 0.687946 1 0.873013 2.566532 0.469760

1 0.324369 -2.988983 0.638025 1 2.190268 2.537996 -1.551555

1 -1.584319 -1.638289 1.987578 1 0.753395 2.450137 -2.586127

6 -2.325691 3.716802 -1.811513 1 2.310265 0.107682 -1.519674

6 -1.951750 2.238425 -1.589131 1 -0.456080 -0.808768 -1.564158

6 -1.025630 2.111397 -0.398302 1 0.650636 -0.204106 -4.337128

6 0.362638 2.234098 -0.429167 1 -0.799999 -2.317396 -4.531178

6 1.216145 2.061529 -1.674841 1 -1.794097 -0.879782 -4.704637

6 1.323059 0.542970 -1.659051 1 -1.782161 -1.758225 -3.160916

6 0.303719 -0.256723 -2.297743 1 -1.584678 0.047600 -0.098441

int3:

44 -0.004149 -0.002206 -0.014177 6 -1.794485 1.443288 0.206505

6 -0.112452 -0.052293 2.305420 6 -1.631340 2.899687 0.532597

6 1.258888 0.112617 1.910763 1 2.055368 1.701336 -4.898624

S34

6 1.641109 -1.052731 1.171909 1 3.080180 0.602660 -3.967848

6 0.512938 -1.961585 1.152549 1 1.635728 -0.014952 -4.784699

6 -0.562909 -1.344507 1.852323 1 0.186295 1.404540 -3.281622

1 -0.679677 0.641439 2.905955 1 1.617023 2.026572 -2.472913

1 1.890769 0.954813 2.143537 1 2.225189 -0.278319 -1.676320

1 2.622566 -1.250395 0.769311 1 0.673843 -2.076803 -1.696045

1 0.508611 -2.951883 0.724095 1 -1.216491 -0.418092 -3.441648

1 -1.533022 -1.777625 2.042554 1 -1.474964 -2.046230 -2.796316

6 2.043544 0.835960 -4.230310 1 -2.427521 -1.079187 -0.726813

6 1.203614 1.147408 -2.976242 1 -1.362076 1.601363 -1.897580

6 1.225020 -0.037486 -2.032744 1 -2.381832 0.861820 0.914220

6 0.322925 -1.103911 -2.024755 1 -2.619081 3.378747 0.542647

6 -1.102040 -1.049833 -2.556374 1 -1.004847 3.415398 -0.198632

6 -1.757941 -0.465386 -1.322043 1 -1.196623 3.043749 1.524912

6 -1.679543 0.936217 -1.101205 1 0.718584 1.367731 -0.321049

ts34:

44 0.004675 0.006191 0.004821 6 0.876846 2.035030 -0.715711

6 -0.012749 -0.047542 2.376591 6 1.828223 2.556959 -1.787416

6 1.332576 -0.017370 1.922665 1 -0.891368 -1.086541 -5.374005

6 1.580193 -1.222810 1.140487 1 -2.111753 -1.737379 -4.268903

6 0.370855 -1.966349 1.098381 1 -0.470098 -2.401920 -4.269987

6 -0.636518 -1.222014 1.832473 1 -1.204271 0.475831 -3.484970

1 -0.488805 0.688833 3.005921 1 0.427238 -0.194001 -3.460500

1 2.071503 0.729879 2.169576 1 -0.499266 -2.013829 -1.821566

1 2.524948 -1.516144 0.710871 1 -2.261832 -1.451974 -0.375682

1 0.229622 -2.924208 0.621812 1 -3.548087 0.539706 -0.301577

1 -1.641636 -1.556066 2.036413 1 -2.961947 1.081057 -1.876727

6 -1.052657 -1.480334 -4.366619 1 -1.768201 1.968040 0.765073

6 -0.630491 -0.439685 -3.312005 1 -0.682892 1.723079 -2.117131

6 -0.855615 -0.988756 -1.913784 1 1.107853 2.406171 0.280848

6 -1.887324 -0.661322 -1.017812 1 1.702924 3.642506 -1.860361

6 -2.652116 0.667580 -0.910725 1 1.621609 2.119498 -2.767204

6 -1.596914 1.525890 -0.210402 1 2.869488 2.356682 -1.526478

6 -0.519249 1.864362 -1.054323 1 1.322552 0.657781 -0.834424

int4:

44 -0.003992 0.053111 -0.038715 6 -2.930678 -1.313568 -0.790772

6 -0.061624 0.019945 2.280970 6 -4.053546 -1.561839 -1.816114

6 1.304460 -0.050563 1.838750 1 -0.748386 4.095033 0.274380

6 1.455165 -1.261558 1.071895 1 0.783167 3.435942 0.875383

6 0.174315 -1.913961 1.017630 1 0.742994 4.352498 -0.641651

6 -0.765489 -1.117678 1.777546 1 -0.806969 1.724456 -0.156424

1 -0.487979 0.806361 2.885978 1 -0.654316 2.521611 -1.713463

1 2.091169 0.640492 2.096901 1 2.095715 1.819522 -0.602676

1 2.370775 -1.629605 0.635411 1 2.126632 -0.086214 -2.080871

1 -0.027958 -2.867500 0.555700 1 -0.483623 0.954044 -3.300217

1 -1.796658 -1.362242 1.970861 1 0.454377 -0.451062 -3.815828

6 0.195446 3.634046 -0.024903 1 -0.524002 -1.864494 -2.052961

6 -0.042400 2.350279 -0.822173 1 -2.260471 0.626487 -1.579114

6 1.173750 1.538513 -1.104714 1 -3.365707 -0.885789 0.118467

6 1.192689 0.461981 -1.992302 1 -2.469084 -2.267609 -0.513444

6 0.074798 0.083734 -2.942547 1 -4.546164 -0.627067 -2.102333

6 -0.767591 -0.804439 -2.049675 1 -4.814272 -2.222445 -1.390970

6 -1.888051 -0.373547 -1.353621 1 -3.664785 -2.031705 -2.724554

S35

XV. References. 1 H. Rakoff, E. A. Emken, Chem. Phys. Lipids, 1982, 31, 215.

2 J. Frisch et al., Gaussian 09, Revision D.01, Gaussian, Inc., Wallingford CT, 2009.

3 A. D. Becke, J. Chem. Phys. 1993, 98, 5648.

4 C. Lee, W. Yang and R. G. Parr, Phys. Rev. B 1988, 37, 785.

5 M. Couty, M. B. Hall, J. Comput. Chem. 1996, 17, 1359.

6 S. Miertuš, E. Scrocco and J. Tomasi Chem. Phys. 1981, 55, 117.

7 J. Tomasi, B. Mennucci and R. Cammi, Chem. Rev. 2005, 105, 2999.

8 G. Scalmani, M. J. Frisch, J. Chem. Phys. 2010, 132, 114110.

9 A. Karton, A. Tarnopolsky, J.-F. Lamère, G. C. Schatz and J. M. L. Martin, J. Phys. Chem. A 2008, 112, 12868.

10 S. Kozuch, J. M. L. Martin, J. Comp. Chem. 2013, 34, 2327.

supporting information for alkene-assisted cis-to-trans ...similar to cis-to-trans isomerization of...

Documents